CHKMISTKY. 277 



On the reversible additiou of alcohol to nitrilcs catiilyzecl by ethylatcs. By E. K. Mar- 

 shall, jr., and 8. F. Acree. American Chemical Journal, 49, 127. 



Dr. Marshall has shown that the twelve nitriles studied by us do 

 not add alcohols, and the imido esters do not lose alcohol with any 

 appreciable velocity, unless catalj'zed by sodium, potassium, lith- 

 ium, thallium, or other ethylates. The reaction has been found 

 reversible in every case studied, and the equilibrium point is the 

 same, whether measured from the nitrile or from the imido ester, 

 although disturbing side reactions make the agreement in some cases 

 less satisfactory than desired. The equilibrium point varies widely 

 with the different compounds, the percentage of imido ester formed 

 being illustrated by the following examples: butyronitrile,0.90; pro- 

 pionitrile, 1.75; acetonitrile, 2.50; p-tolunitrile, 6.8; benzonitrile, 

 14.0; p-brombenzonitrile, 27.2; ??z-brombenzonitrile, 38; p-nitro- 

 benzonitrile, 62.0; ??i-nitrobenzonitrile, 78.0; diisoamjdcj^anoamide, 

 98.0. A few of these experiments given in this article and in other 

 unpublished work show that the reaction velocity can be expressed 

 as a function of the concentration of both the ethylate ions and the 

 nonionized salts. 



On the reactions of both the ions and the non-iouizcd forms of electrolytes. By S. F. 

 Acree. American Chemical Journal, 49, 345. 



In this article is presented a large amount of original material and 

 a reinterpretation of the work of Arrhenius, Ostwald, Goldschmidt, 

 Bredig, Stieglitz, Holmberg, van Dam, Koelichen, and others, who 

 had assumed that only the ions are chemically active. It is shown 

 that the discrepancies in their work and theories can be accounted for 

 very easil}^ bj^ our theory that, in all these cases, the activity of both 

 the ions and the non-ionized electrolytes must be considered. A 

 large number of calculations are given in support of the newer point 

 of view. 



On the reactions of both the ions and the nonionized forms of electrolytes. The reversi- 

 ble addition of alcohol to nitriles catalj'zed by sodium ethylate. ByE. K. Marshall, 

 jr., Julia P. Harrison, and S. F. Acree. American Chemical Journal, 49, 369. 



In this article is given an accurate quantitative study of the 

 velocity of the reversible decomposition of acetimido ethyl ester and 

 ])enzimido ethyl ester into ethyl alcohol and the corresponding 

 nitriles at 25° in the presence of sodium ethylate in varying concen- 

 trations. The data show clearly that the reaction velocities can be 

 expressed as a function of the concentrations of both the ethylate 

 ions and the nonionized sodium ethylate. We obtained for benz- 

 imido ethyl ester the values Ki = 0.1172 and K,„ = 0.0976, and for 

 acetimido ethyl ester the constants Kt = 0.344, and K„ = 0.288. 



A recalculation of the work of Stieglitz and Schlesinger on the 

 decomposition of imido esters by barium hydroxide shows that their 

 theory, that only the hydroxyl ions act catalytically, is untenable. 



